Biophysical Chemistry
1st Edition
Thermodynamics, Electrostatics, and the Biological Significance of the Properties of Matter
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Description
Biophysical Chemistry, Volume I: Thermodynamics, Electrostatics, and the Biological Significance of the Properties of Matter focuses on the biological aspects of the properties of matter, putting emphasis on the chemical elements, water and carbon dioxide, complex molecules, and proteins.
The publication first elaborates on biochemistry and geochemistry, water and its biological significance, and the problems of protein structure. Discussions focus on the number of peptide chains in the molecule and nature of terminal groups, latent heat of fusion, characteristics of the amino acids derived from proteins, expansion of water in freezing, and the relative abundance of chemical elements in the universe. The text then takes a look at thermodynamics and the application to polar molecules and ionic solutions of electrostatics, including free energy of a charged sphere, image charges, salting-out effect, expressions for the change of fundamental thermodynamic functions, and chemical potentials.
The book examines the conductivity of electrolytes, acid-base equilibria, and polybasic acids, bases, and ampholytes, including proteins. Topics include ionization of cysteine, isoelectric points of polyvalent ampholytes, hemoglobin, nature of acids and bases, measurement of conductivity, electrolytes as conductors, and the moving boundary method of determining transference numbers.
The manuscript is a dependable reference for chemists and researchers interested in thermodynamics, electrostatics, and the biological value of the properties of matter.
Table of Contents
Preface
Symbols
1. Biochemistry and Geochemistry
Distribution of the Chemical Elements in Living Organisms
The Relative Abundance of the Chemical Elements in the Universe
The Structure of the Earth and Its Crust
Early History of the Earth
The Ocean
The Central Role of Carbon in Biology
References
2. Water and Its Biological Significance
Heat Capacity of Water and Other Substances
Heat of Vaporization
Latent Heat of Fusion
The Expansion of Water in Freezing
Surface Tension
Dielectric Constant of Water
Solubility
References
3. Problems of Protein Structure
Proteins; Some General Considerations
Amino Acids and Peptides as Dipolar Ions
Characteristics of the Amino Acids Derived from Proteins
Amino Acid Analysis of Proteins
Polypeptide Chains and Their Presence in Proteins
Determination of Arrangement of Peptide Chains and Their Linkage within Protein Molecules
The Number of Peptide Chains in the Molecule, and the Nature of the Terminal Groups
Cross-Linkages Between Peptide Chains: Disulfide and Phosphate Cross-Linkages
Phosphate Cross-Linkages
Other Cross-Linkages
Sequence of Amino Acid Residues in Peptide Chains
Disulfide Linkages in Insulin and Ribonuclease
Spatial Configurations of Polypeptide Chains
Silk Fibroin
β-Keratin
α-Keratin and Synthetic Polypeptides: the α-Helix and Other Possible Helical Structures
Collagen
Amino Acid Composition
Heat Shrinkage
The Structural Pattern—Evidence from X-Ray and Electron Microscope Studies
Collagen Structure
The Stability of Helical Structures
The Significance of Disulfide Bonds; Cross-Linkages and Loops in Peptide Chains
Possible Stereochemistry of Insulin
Stereochemistry and Enzyme Activity of Ribonuclease
Helical and Nonhelical Regions in Globular Proteins
References
4. Thermodynamics
Introduction
Systems and Phases
Temperature
Dimensions of Temperature
First Law
Second Law
Irreversible Processes
Maximum Work, Equilibrium, and Free Energy
Heat Content, or Enthalpy
Expressions for the Change of the Fundamental Thermodynamic Functions
Partial Molal Quantities
Chemical Potentials
Phase Rule
Activities
Ideal or Perfect Solutions and Raoult's Law
Activity Coefficients and the Choice of Standard States
Activity and Chemical Potential of a Nonvolatile Solute from the Vapor Pressure of the Solvent
Equilibrium Between Phases; Activities in Relation to Distribution Coefficients and Solubilities
Activity of Strong Electrolytes
Mass Law
The Malate-Fumarate Equilibrium
Peptide Bond Synthesis in the Reaction Between Benzoyl-L-Tyrosine and Glycinamide
The Standard Free Energy of Hydrolysis of Adenosine Triphosphate
Systems Involving Other Variables
Elastic Bodies
Systems in Gravitational or Centrifugal Fields
Statistical Interpretation of Entropy
Entropy of a Perfect Crystal at 0°K
Entropy Change on Mixing of Components in an Ideal Solution
The Residual Entropy of Ice
Standard Free Energies of Formation and Their Use in Determining Thermodynamic Equilibria
The Fumarate-Malate Equilibrium
The First Ionization of Carbonic Acid
Standard Free Energy of Peptide Bond Synthesis
References
5. Electrostatics: Its Application to Polar Molecules and Ionic Solutions
Definition of the Potential
Gauss's Law
Poisson's Equation for Regions Containing a Space Charge
Free Energy of a Charged Sphere
The Potential and Energy of a Dipole
Image Charges
The Salting-Out Effect
Salting Out of Proteins
Effects of Dipolar Ions
Debye's Theory of Salting Out by Redistribution of Solvent Molecules Around the Ions
Ionic Interactions and the Debye-Hückel Theory
Ion-Dipole Interactions
Experimental Studies on the Solubility of Dipolar Ions, and Their Interaction with Ions
Solubilities and Activity Coefficients in Water and Other Media
Solubilities in the Presence of Salt
References
6. Dielectric Constants and Their Significance
Introduction to Dielectric Constants and Dipole Moments
Dielectric Polarization in Relation t o Molecular Properties
The Debye Theory of the Dielectric Constant
Application of the Debye Theory
The Breakdown of the Debye Theory in Polar Liquids
Modifications of the Debye Theory
The Onsager Theory
Kirkwood's Theory
Polar Liquids and Dipolar Ions
Dielectric Constants and Dipole Moments of Dipolar Ions in Solution
Methods of Measuring Dielectric Constant
References
7. Conductivity of Electrolytes
Conductance and Resistance
Electrolytes as Conductors
Faraday's Law
Equivalent Conductivity
Ion Mobilities
Ion Conductances
Transference Numbers
Hittorf Method of Determining Transference Numbers
The Moving Boundary Method of Determining Transference Numbers
Theoretical Considerations Regarding Equivalent Conductance; Effects of Interionic Forces
Measurement of Conductivity
References
8. Acid-Base Equilibria
The Nature of Acids and Bases
The Concept of pH; a Preliminary Statement
Calculations of pH in Systems of Acids of Known Acid Strengths
The Titration of a Weak Acid with a Strong Base; Buffer Action
The Experimental Determination of Acidity Constants (KA Values)
The Conductivity Method
The Indicator Method for Determining Relative Strengths of Acids
Electromotive Force Measurements and pH Determination
Standard Potentials of Half-Cells, Choice of Conventions
Evaluation of pKA from Cells without Liquid Junction
Cells Containing Liquid Junctions
The Liquid Junction Potential
Variation of pH with Ionic Strength for Acid-Base Pairs of Different Charge Types
Choice of a Standard for Calibrating pH Measurements
The Glass Electrode
Determination of pKA Values and Related Thermodynamic Functions in Relation to Structure
Effect of Neighboring Charged Groups and Dipoles on pKA Values
Other Acidic Groups of Biochemical Interest
Phenolic Hydroxyl Groups
Imidazole Groups
Sulfhydryl Groups
The Guanidinium Group
The Peptide Linkage
Purines, Pyrimidines, Nucleosides, and Nucleotides
Effects of Variation in Dielectric Constant of Solvent on Relative Strength of Acids of Different Charge Types
Problems
References
9. Polybasic Acids, Bases, and Ampholytes, Including Proteins
Dibasic Acids
Polyvalent Acids: General Relations
A Specific Case: Glutamic Acid
Spectroscopic Determination of Microscopic Constants: The Ionization of Cysteine
Isoelectric Points of Amphoteric Substances
Isoelectric Points of Polyvalent Ampholytes
Equilibrium Between Different Ionic Forms in Polyvalent Acids and Ampholytes: The Equation of Linderstrøm-Lang
Electrostatic Effects on Ionization in Polybasic Acids. The Charged Sphere Model
Formulation in Terms of Association Constants
Acid-Base Equilibria in β-Lactoglobulin Solutions
Ovalbumin
Serum Albumins
Ribonuclease
Hemoglobin
Other Proteins
Synthetic Polyelectrolytes, Including Polypeptides
Effects of Internal Hydrogen Bonding on Titration Curves
Calculations with a Dielectric Sphere Model Containing Fixed Charges
References
10. Carbon Dioxide and Carbonic Acid
Carbon Dioxide in Nature
Structural Considerations
The Fundamental Equilibria in Systems Containing Carbon Dioxide and Carbonic Acid
Absorption Coefficients of Carbon Dioxide in Water
The Reversible Hydration of Carbon Dioxide and the Ionization of Carbonic Acid
Carbon Dioxide Dissociation Curves
The Formation of Carbamates
Rates of the Reactions CO2 + H2O → H2CO3
The Velocity of the Dehydration Reaction: H2CO3 → H2O + CO2
The Hydration Reaction: CO2 + H2O → H2CO3
Carbonic Anhydrase
References
11. Some General Aspects of Molecular Interactions
Some Methods of Measuring Binding
Equilibrium Dialysis
Ultrafiltration
Spectroscopic Measurements
Electromotive Force Measurements
Ultracentrifuge Measurements
Electrophoresis
Effects of pH Changes When Salts Are Added: Isoionic Points
Isoelectric and Isoionic Solutions
Some Fundamental Considerations Regarding Certain Types of Binding
Interactions of Bound Groups
Competition Effects
Interactions Between Different Kinds of Bound Groups
Formation of Chelate Complexes
Binding by a Set of Equivalent and Independent Groups
The Logarithmic Plot: Bjerrum's "Formation Function"
The Reciprocal Plot
The Scatchard Plot of v/(A) against v
Relation of Equations for Binding to Those of Enzyme Kinetics
General Equation for Binding by a Molecule or Ion with n Sites Available for Combination
Binding by an Equivalent Set of Groups with Interactions Between Them
Complexes of Biochemical Substances with Metallic Ions: Some General Considerations
Electrostatic Effects on Binding of Ions
Effects of Competition Between Different Ligands for the Same Binding Site
Linked Functions
References
Details
- No. of pages:
- 716
- Language:
- English
- Copyright:
- © Academic Press 1958
- Published:
- 1st January 1958
- Imprint:
- Academic Press
- eBook ISBN:
- 9781483270586
About the Authors
John Edsall
Affiliations and Expertise
Biological Laboratories Harvard University Cambridge, Massachusetts
Jeffries Wyman
Ratings and Reviews
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